WO2019034149A1

WO2019034149A1 - Catalyst for preparing propylene glycol phenyl ether and method for synthesizing propylene glycol phenyl ether

Info

Publication number: WO2019034149A1
Application number: PCT/CN2018/101121
Authority: WO
Inventors: 梁国强
Original assignee: 佳化化学（茂名）有限公司
Priority date: 2017-08-18
Filing date: 2018-08-17
Publication date: 2019-02-21
Also published as: EP3626340A4; CN107694602A; US20200157030A1; EP3626340A1; CN107694602B; EP3626340B1; PL3626340T3; US11091416B2

Abstract

Disclosed is the use of a quaternary phosphonium salt compound as a catalyst for preparing a catalyst for propylene glycol phenyl ether. Also provided is a method for synthesizing propylene glycol phenyl ether by mixing phenol and a quaternary phosphonium salt compound, and then adding propylene oxide under oxygen-free conditions, wherein the phenol is polymerized with the propylene oxide to produce the propylene glycol phenyl ether. The propylene glycol phenyl ether thus prepared has few impurities and contains no metal ions, such as potassium and sodium, and does not require subsequent operations to remove metal ions and perform rectification separation, thereby reducing the costs and allowing same to be directly applied to high-standard industrial production.

Description

Catalyst for preparing propylene glycol phenyl ether and synthesis method of propylene glycol phenyl ether

Technical field

The invention belongs to the technical field of chemical industry, and particularly relates to a catalyst for preparing propylene glycol phenyl ether and a method for synthesizing propylene glycol phenyl ether.

Background technique

Propylene glycol phenyl ether is a colorless transparent liquid with mild odor and non-toxic and environmentally friendly properties. Propylene glycol phenyl ether is a typical high-efficiency film-forming auxiliary. After adding the latex system, it can be redistributed in the aqueous phase and the polymerization phase. Its partition coefficient in the two phases is extremely small, thus ensuring excellent film forming performance and good performance. The plasticizing effect and the appropriate evaporation rate balance. Propylene glycol phenyl ether has a strong solubility for most latexes, and its water-soluble properties ensure that it is completely absorbed by the latex particles, giving the latex paint the best color uniformity and coalescence. Excellent storage stability. Propylene glycol phenyl ether can also be used as an excellent high-boiling organic solvent and modifier to replace the solvent of isophorone, cyclohexanone, benzyl alcohol or ethylene glycol phenyl ether. Due to its non-toxicity, good miscibility, moderate volatilization rate, excellent coalescence and coupling ability, low surface tension, it is widely used in automotive and automotive refinish coatings, electrophoretic coatings, industrial baking varnishes and ships, containers, wood coatings, etc. field.

At present, the production of propylene glycol phenyl ether generally adopts two synthetic processes, one is to produce propylene glycol phenyl ether by using chloropropanol and phenol as a reaction substrate, but chloropropanol is used as a substrate, and a large amount of waste is easily generated. The second method for synthesizing propylene glycol phenyl ether is to carry out ring-opening polymerization of phenol and propylene oxide (PO) to form propylene glycol phenyl ether under the catalysis of a basic catalyst such as sodium hydroxide or potassium hydroxide. The method is an industrial production method mainly used at present, but the catalyst is used to catalyze the synthesis of the product. The product propylene glycol phenyl ether also contains metal ions such as potassium metal and sodium ions, and cannot be directly applied to industrial fields where metal ions are strictly restricted. Subsequent processing of the product is required to remove metal ions, complicating the operation of the entire process and increasing the production cost of propylene glycol phenyl ether.

Summary of the invention

The technical problem to be solved by the invention is to overcome the metal ion contained in the propylene glycol phenyl ether catalyzed by the catalyst in the prior art, and can not be directly applied to the industrial field where the metal ion is strictly restricted, and the subsequent metal ion removal operation leads to the whole process. The operation process is complicated and the production cost is increased. There is thus provided a catalyst capable of producing propylene glycol phenyl ether which is free of metal ions and which does not require subsequent metal ion removal operations.

To this end, the first aspect of the invention provides the use of a quaternary phosphonium salt compound as a catalyst for the preparation of propylene glycol phenyl ether.

The above quaternary phosphonium salt compound is used as a catalyst for preparing propylene glycol phenyl ether. Preferably, the quaternary phosphonium salt compound is selected from the group consisting of methyl triphenylphosphonium bromide, ethyl triphenylphosphonium bromide, and propyl three. Any one or a combination of phenylphosphonium bromide or butyltriphenylphosphonium bromide.

The above quaternary phosphonium salt compound is preferably used as a catalyst for preparing propylene glycol phenyl ether, and the molar fraction of any one of the components is from 1 to 99 parts.

A second aspect of the present invention provides a method for synthesizing propylene glycol phenyl ether, comprising the steps of: mixing phenol with the above quaternary phosphonium salt compound, and then adding propylene oxide under anaerobic conditions, the phenol and the ring The oxypropane is polymerized to form the propylene glycol phenyl ether.

In the above method for synthesizing propylene glycol phenyl ether, preferably, the molar ratio of the phenol to the propylene oxide is 1: (1-1.15).

In the above method for synthesizing propylene glycol phenyl ether, preferably, the quaternary phosphonium salt compound is added in an amount of from 0.05% to 0.3% by mass of the phenol to the propylene oxide.

In the above method for synthesizing propylene glycol phenyl ether, preferably, the polymerization reaction is carried out under the conditions of a temperature of 100 to 160 ° C and a pressure of ≤ 1.0 MPa.

The method for synthesizing the above propylene glycol phenyl ether preferably further comprises: adding the temperature to 80 ° C before the step of adding the propylene oxide, then controlling the temperature to 80 to 160 ° C, the pressure ≤ 1.0 MPa, adding the The step of propylene oxide.

The method for synthesizing the above propylene glycol phenyl ether preferably further comprises: after adding propylene oxide, controlling the temperature at 100 to 160 ° C, and aging for 2 to 10 hours to obtain the propylene glycol phenyl ether; and then controlling the temperature at 100 to 130 ° C, And the step of vacuuming at 100 to 130 °C.

The present invention has the following advantages over the prior art:

1. The use of the quaternary phosphonium salt compound provided by the invention as a catalyst for preparing propylene glycol phenyl ether, the quaternary phosphonium salt compound as a catalyst has high catalytic efficiency, and the catalytically synthesized propylene glycol phenyl ether does not contain metal ions such as potassium and sodium. Improve the quality and environmental friendliness of synthetic products. After the synthesis of propylene glycol phenyl ether by using the quaternary phosphonium salt catalyst, the subsequent operation of removing metal ions is not required, which simplifies the production process and reduces the production cost. The quaternary phosphonium salt compound has high relative stability as a catalyst, and the quality of the catalytically synthesized propylene glycol phenyl ether is stable, the repeatability between batches is good, and the requirements for the reaction conditions and the strength of the equipment are lowered.

2. The quaternary phosphonium salt compound provided by the present invention as a catalyst for preparing propylene glycol phenyl ether is methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide or butyltriphenylbenzene. Any one or a combination of the above-mentioned compounds as a catalyst for preparing propylene glycol phenyl ether, which has the characteristics of high thermal stability, easy availability, no pollution, and no need to separate from the product. It is an economical and environmentally friendly catalyst that can reduce the synthesis cost of propylene glycol phenyl ether and promote the environmental impact of the synthesis process.

3. The method for synthesizing propylene glycol phenyl ether provided by the present invention, by using the above quaternary phosphonium salt compound as a reaction catalyst, the synthesized propylene glycol phenyl ether does not contain metal ions, and does not require subsequent metal ion removal operation, thereby improving product quality. It simplifies the operation process of the entire synthesis process and reduces the production cost of propylene glycol phenyl ether.

4. The method for synthesizing propylene glycol phenyl ether provided by the invention reduces the addition of the catalyst under the premise of ensuring the catalytic activity and product quality of the catalyst by controlling the reaction temperature, pressure, time, and the ratio of addition of phenol and propylene oxide. The amount of propylene glycol phenyl ether produced by the above method is small, and does not require a subsequent rectification purification step, and can be directly applied to industrial production and application.

5. The method for synthesizing propylene glycol phenyl ether provided by the present invention ensures high catalytic activity of the catalyst by controlling the temperature and pressure of the reaction, and the vacuuming step after the end of the reaction effectively removes the substrate which is not completely reacted.

Detailed ways

The embodiments of the present invention are illustrated by the following specific examples. Unless otherwise stated, the experimental methods disclosed in the present invention are all based on the conventional techniques in the art, and the reagents and raw materials used in the examples are commercially available.

Example 1

The present embodiment provides a method for synthesizing propylene glycol phenyl ether, which specifically comprises the following steps:

(1) In a 2-liter autoclave, 10 mol of phenol was added; and 10 mol of propylene oxide was added to the metering tank.

(2) The catalyst was continuously added to the reaction vessel: methyltriphenylphosphonium bromide, and the amount of the catalyst added was 0.05% of the sum of the masses of phenol and propylene oxide. After the kettle was closed, the mixture was purged with nitrogen, and then the temperature was raised to 80 ° C. The propylene oxide in the metering tank was started to be added to the reaction vessel to continue the temperature rise, and the reaction temperature was controlled at 100 to 110 ° C, and the reaction pressure was ≤ 1.0 MPa.

(3) After the addition of propylene oxide, the propylene oxide feed valve is closed, and the temperature is maintained at 100 to 110 ° C for 8 hours. After the completion of the reaction, the temperature was controlled to 100 to 110 ° C, and evacuation was carried out for 1 hour. The temperature is lowered to below 80 ° C to obtain a propylene glycol phenyl ether product.

Example 2

(1) In a 2-liter autoclave, 10 mol of phenol was added; and 10.3 mol of propylene oxide was added to the metering tank.

(2) The catalyst was continuously added to the reaction vessel: ethyltriphenylphosphonium bromide, and the amount of the catalyst added was 0.2% of the sum of the masses of phenol and propylene oxide. After the kettle was closed, the mixture was purged with nitrogen, and then the temperature was raised to 80 ° C. The propylene oxide in the metering tank was started to be added to the reaction vessel to continue the temperature rise, and the reaction temperature was controlled at 100 to 110 ° C, and the reaction pressure was ≤ 1.0 MPa.

(3) After the addition of propylene oxide, the propylene oxide feed valve is closed, and the temperature is maintained at 130 to 140 ° C for 4 hours. After the end of the reaction, the temperature was controlled to 110 to 120 ° C, and evacuation was carried out for 2.5 hours. The temperature is lowered to 80 ° C to obtain a propylene glycol phenyl ether product.

Example 3

(1) In a 2-liter autoclave, 10 mol of phenol was added; and 10.5 mol of propylene oxide was added to the metering tank.

(2) The catalyst was continuously added to the reaction vessel: propyltriphenylphosphonium bromide, and the amount of the catalyst added was 0.3% of the sum of the masses of phenol and propylene oxide. After the autoclave was replaced with nitrogen, the temperature was raised to 80 ° C, and propylene oxide in the metering tank was started to be added to the reaction vessel to continue the temperature rise, and the reaction temperature was controlled at 150 to 160 ° C, and the reaction pressure was ≤ 1.0 MPa.

(3) After the completion of the addition of propylene oxide, the propylene oxide feed valve is closed, and the temperature is maintained at 150 to 160 ° C for 4 hours. After the end of the reaction, the temperature was controlled to 120 to 130 ° C, and evacuation was carried out for 2 hours. The temperature is lowered to below 80 ° C to obtain a propylene glycol phenyl ether product.

Example 4

(1) In a 2-liter autoclave, 10 mol of phenol was added; and 11 mol of propylene oxide was added to the metering tank.

(2) The catalyst was continuously added to the reaction vessel: butyltriphenylphosphonium bromide, and the amount of the catalyst added was 0.3% of the sum of the masses of phenol and propylene oxide. After the kettle was closed, the nitrogen gas was replaced, and then the temperature was raised to 80 ° C. The propylene oxide in the metering tank was started to be added to the reaction vessel, and the temperature was further raised. The reaction temperature was controlled at 120 to 130 ° C, and the reaction pressure was ≤ 1.0 MPa.

(3) After the completion of the addition of propylene oxide, the propylene oxide feed valve is closed, and the temperature is maintained at 130 to 140 ° C for 2 hours. After the end of the reaction, the temperature was controlled to 110 to 120 ° C, and evacuation was carried out for 3 hours. The temperature is lowered to below 40 ° C to obtain a propylene glycol phenyl ether product.

Example 5

(1) In a 2-liter autoclave, 10 mol of phenol was added; and 11.5 mol of propylene oxide was added to the metering tank.

(2) continuing to add a catalyst to the reaction vessel: a combination of methyltriphenylphosphonium bromide and ethyltriphenylphosphonium bromide, the catalyst is added in an amount of 0.15% of the sum of the masses of phenol and propylene oxide, wherein The molar fraction of methyltriphenylphosphonium bromide was 1 part, and the molar fraction of ethyltriphenylphosphonium bromide was 99 parts. After the kettle was closed, the mixture was purged with nitrogen, and then the temperature was raised to 80 ° C. The propylene oxide in the metering tank was started to be added to the reaction vessel to continue the temperature rise, and the reaction temperature was controlled at 100 to 110 ° C, and the reaction pressure was ≤ 1.0 MPa.

(3) After the completion of the addition of propylene oxide, the propylene oxide feed valve is closed, and the temperature is maintained at 120 to 130 ° C for 4 hours. After the completion of the reaction, the temperature was controlled to 100 to 110 ° C, and evacuation was carried out for 3 hours. The temperature is lowered to below 80 ° C to obtain a propylene glycol phenyl ether product.

Example 6

(1) In a 2-liter autoclave, 10 mol of phenol was added; and 11.3 mol of propylene oxide was added to the metering tank.

(2) continuing to add a catalyst to the reaction vessel: a composition of ethyltriphenylphosphonium bromide and propyltriphenylphosphonium bromide, the catalyst is added in an amount of 0.1% of the sum of the masses of phenol and propylene oxide, wherein The molar fraction of ethyltriphenylphosphonium bromide was 30, and the molar fraction of propyltriphenylphosphonium bromide was 70. After the autoclave was replaced with nitrogen, the temperature was raised to 80 ° C, and propylene oxide in the metering tank was started to be added to the reaction vessel to continue the temperature rise, and the reaction temperature was controlled at 150 to 160 ° C, and the reaction pressure was ≤ 1.0 MPa.

(3) After the addition of propylene oxide, the propylene oxide feed valve is closed, and the temperature is maintained at 100 to 120 ° C for 6 hours. After the end of the reaction, the temperature was controlled at 105 to 115 ° C, and evacuation was carried out for 3 hours. The temperature is lowered to below 80 ° C to obtain a propylene glycol phenyl ether product.

Example 7

(1) In a 2-liter autoclave, 10 mol of phenol was added; and 10.1 mol of propylene oxide was added to the metering tank.

(2) continuing to add a catalyst to the reaction vessel: a combination of methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, and butyltriphenylphosphonium bromide, The amount of the catalyst added is 0.3% of the sum of the masses of phenol and propylene oxide, wherein the molar fraction of methyltriphenylphosphonium bromide is 1, and the molar fraction of ethyltriphenylphosphonium bromide is 25, propyl. The molar fraction of triphenylphosphonium bromide was 25, and the molar fraction of butyltriphenylphosphonium bromide was 49. After the autoclave was replaced with nitrogen, the temperature was raised to 80 ° C, and propylene oxide in the metering tank was started to be added to the reaction vessel to continue the temperature rise, and the reaction temperature was controlled at 150 to 160 ° C, and the reaction pressure was ≤ 1.0 MPa.

Test example 1

The content of metal ions in the propylene glycol phenyl ether prepared in Example 1 - Example 7 was determined by flame photometer analysis, and the results were examined using an AquaTint automatic colorimeter (purchased from Roewe, Germany) in Example 1 - Example 7. The color of the prepared product, the results are shown in Table 1:

Table 1 Test results of propylene glycol phenyl ether prepared by the synthesis method described in Example 1 - Example 7

It can be seen from Table 1 that the propylene glycol phenyl ether is catalyzed by a quaternary phosphonium salt catalyst, and the potassium and sodium ions in the product are all 0, no need to remove potassium, sodium or rectification, and propylene glycol phenyl ether can be directly applied to the concentration of metal ions. Strictly restricted industrial areas. At the same time, the synthesis method of the propylene glycol phenyl ether provided above simplifies the operation process of the whole synthesis process, reduces the synthesis cost of the propylene glycol phenyl ether, and the industrial application range of the synthesized propylene glycol phenyl ether is wide.

It is apparent that the above-described embodiments are merely illustrative of the examples, and are not intended to limit the embodiments. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. There is no need and no way to exhaust all of the implementations. Obvious changes or variations resulting therefrom are still within the scope of the invention.

Claims

Use of a quaternary phosphonium salt compound as a catalyst for the preparation of propylene glycol phenyl ether.
The use of the quaternary phosphonium salt compound according to claim 1 as a catalyst for preparing propylene glycol phenyl ether, characterized in that the quaternary phosphonium salt compound is selected from the group consisting of methyltriphenylphosphonium bromide and ethyltriphenyl bromide. Any one or a combination of phosphine, propyltriphenylphosphonium bromide or butyltriphenylphosphonium bromide.
The use of the quaternary phosphonium salt compound according to claim 2 as a catalyst for preparing propylene glycol phenyl ether, characterized in that the molar fraction of any one of the components in the composition is from 1 to 99 parts.
A method for synthesizing propylene glycol phenyl ether, comprising the steps of: mixing phenol with the quaternary phosphonium salt compound according to any one of claims 1 to 3, and then adding propylene oxide under anaerobic conditions; The phenol is polymerized with the propylene oxide to form the propylene glycol phenyl ether.
The method for synthesizing propylene glycol phenyl ether according to claim 4, wherein a molar ratio of the phenol to the propylene oxide is 1: (1-1.15).
The method for synthesizing propylene glycol phenyl ether according to claim 4 or 5, wherein the quaternary phosphonium salt compound is added in an amount of from 0.05% to 0.3% by mass based on the mass of the phenol and the propylene oxide.
The method for synthesizing propylene glycol phenyl ether according to any one of claims 4 to 6, wherein the polymerization reaction is carried out under the conditions of a temperature of 100 to 160 ° C and a pressure of 1.0 MPa.
The method for synthesizing propylene glycol phenyl ether according to claim 7, further comprising: raising the temperature to 80 ° C before the step of adding the propylene oxide, and then controlling the temperature to 80 to 160 ° C, the pressure ≤ 1.0 MPa, the step of adding the propylene oxide.
The method for synthesizing propylene glycol phenyl ether according to claim 8, further comprising: after adding propylene oxide, controlling the temperature at 100 to 160 ° C, and aging for 2 to 10 hours to obtain the propylene glycol phenyl ether; and then controlling The temperature is 100 to 130 ° C, and a vacuum is applied at 100 to 130 ° C.